Abstract
This thesis aims to contribute to the knowledge of the influences of the leonardite iron humates character and their behavior in the soil-plant system as a low-cost and an ecofriendly alternative in iron nutrition for the Strategy I plants when they grow in calcareous soils. Moreover, different methods to improve their efficiency were evaluated. Leonardite iron humates are natural iron complexes commonly used in the Mediterranean basin to fertilize cash crops such as citrus, peach trees, and vineyards (Strategy I plants) by foliar application or by fertirrigation. They are less efficient in correcting iron chlorosis than synthetic iron chelates because their structural and physicochemical complexity depends on the diagenetic process which originated them. Currently, the fertilizer market offers only a few iron humates as correctors of iron deficiency because of the strict legal requirements at the European and Spanish regulations. However, due to the new European directives in micronutrient fertilizers and the need to reduce the environmental impact of current agricultural practices, the discussion about the effectiveness of these products is renewed as well as the opportunity to increase their use and commercialization. Therefore, two types of leonardite, one of African origin and another of German origin, were exhaustively characterized. Both products presented ferrihydrite and polynuclear iron compounds in their structures. In particular, the African one presented jarosite in its structure. Moreover, iron humates were also characterized to assess their stability and solubility under calcareous conditions. The kinetic behavior of the iron humate has been studied by ligand competition experiments using chelating agents such as o,oEDDHA, HBED, and BPDS. Iron humate presented high stability. Iron humates exert a long-term effect on the iron fertilization of Strategy I plants in hydroponics (soybean) or soil experiment under controlled conditions as well as in field experiments (tangerines). Deposition and accumulation of humates and iron in the soybean roots were observed in hydroponic assays, and that affected on plant growth as well as in iron nutrition. So, as a first step in improving iron humates, the application mode and the concentration used were studied and corrected. Consequently, iron humates were so efficient at long term as iron synthetic chelates in providing iron ton soybean plants. Furthermore, iron humates from the African leonardite produced jarosite deposits in the soybean roots, which was considered a potentially and bioavailable iron source for the nutritional demands of plants. As a second option in improving the iron humates efficiency, mixtures of iron humates with synthetic iron chelates in different ratios and doses were prepared and applied to soybean plants that grew in calcareous conditions. The mixtures were prepared using stable iron isotopes (56Fe and 57Fe) in order to identify the contribution of each fertilizer to the iron nutrition. The iron chelate shuttle effect was low but improved iron humate efficiency and a slight synergy between iron humates and HBED/Fe3+ was observed because of its lasting effects fit better to the iron humate long-term effect. Finally, leonardite iron humate nanofertilizers were prepared as an improvement option by decreasing particle size. Their contribution to iron nutrition was confirmed and their presence in soybean pods was observed. Although the nanofertilizers did not enhance the iron humate efficiency, they are part of novel technology in line with precision and sustainable agriculture so, further research is needed.
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Claims 13
Claim · model-written summary
Both leonardite products contained ferrihydrite and polynuclear iron compounds.
- Taxon
- soybean
Glycine maxe1 - Outcome
- ferrihydrite and polynuclear iron compoundse0
Organisms pictured · Representative pictures of the matched species, not figures from the paper.

Verbatim
e0“Both products presented ferrihydrite and polynuclear iron compounds in their structures”
t0“strategy i plants”
e1“Iron humates exert a long-term effect on the iron fertilization of Strategy I plants in hydroponics (soybean) or soil experiment under controlled conditions as well as in field experiments (tangerines)”
Claim · model-written summary
African leonardite contained jarosite.
- Taxon
- soybean
Glycine maxe1 - Outcome
- jarositee0
Organisms pictured · Representative pictures of the matched species, not figures from the paper.

Verbatim
e0“the African one presented jarosite in its structure”
t0“strategy i plants”
e1“Iron humates exert a long-term effect on the iron fertilization of Strategy I plants in hydroponics (soybean) or soil experiment under controlled conditions as well as in field experiments (tangerines)”
Claim · model-written summary
Iron humate had high stability.
- Taxon
- soybean
Glycine maxe1 - Outcome
- high stabilitye0
Organisms pictured · Representative pictures of the matched species, not figures from the paper.

Verbatim
e0“Iron humate presented high stability”
t0“strategy i plants”
e1“Iron humates exert a long-term effect on the iron fertilization of Strategy I plants in hydroponics (soybean) or soil experiment under controlled conditions as well as in field experiments (tangerines)”
Claim · model-written summary
Iron humates exerted a long term effect on plant iron fertilization.
- Taxon
- soybean
Glycine maxe0 - Treatment
- Iron humatese0
- Outcome
- iron fertilizatione0
- Setting
- hydroponicse0
Not reportedComparatorDirection
Organisms pictured · Representative pictures of the matched species, not figures from the paper.

Verbatim
e0“Iron humates exert a long-term effect on the iron fertilization of Strategy I plants in hydroponics (soybean) or soil experiment under controlled conditions as well as in field experiments (tangerines)”
Claim · model-written summary
Humates and iron accumulated in soybean roots.
- Taxon
- soybean
Glycine maxe0 - Organ / stage
- soybean rootse0
- Outcome
- Deposition and accumulation of humates and irone0
- Setting
- hydroponic assayse0
Organisms pictured · Representative pictures of the matched species, not figures from the paper.

Verbatim
e0“Deposition and accumulation of humates and iron in the soybean roots were observed in hydroponic assays”
Claim · model-written summary
Iron humates matched synthetic chelates in long term iron provision to soybean.
- Taxon
- soybean
Glycine maxe0 - Treatment
- iron humatese0
- Outcome
- providing iron ton soybean plantse0
- Direction
- so efficiente0
- Comparator
- iron synthetic chelatese0
Organisms pictured · Representative pictures of the matched species, not figures from the paper.

Verbatim
e0“iron humates were so efficient at long term as iron synthetic chelates in providing iron ton soybean plants”
Claim · model-written summary
African iron humate produced jarosite deposits in soybean roots.
- Taxon
- soybean
Glycine maxe0 - Treatment
- iron humates from the African leonarditee0
- Outcome
- jarosite deposits in the soybean rootse0
Not reportedComparatorDirection
Organisms pictured · Representative pictures of the matched species, not figures from the paper.

Verbatim
e0“iron humates from the African leonardite produced jarosite deposits in the soybean roots”
Claim · model-written summary
Iron chelate shuttle effect was low.
- Taxon
- soybean
Glycine maxe1 - Outcome
- iron chelate shuttle effecte0
Organisms pictured · Representative pictures of the matched species, not figures from the paper.

Verbatim
e0“The iron chelate shuttle effect was low”
t0“strategy i plants”
e1“Iron humates exert a long-term effect on the iron fertilization of Strategy I plants in hydroponics (soybean) or soil experiment under controlled conditions as well as in field experiments (tangerines)”
Claim · model-written summary
Iron chelate improved humate efficiency.
- Taxon
- soybean
Glycine maxe1 - Treatment
- iron chelatee2
- Outcome
- iron humate efficiencye0
- Direction
- improvede0
Not reportedComparator
Organisms pictured · Representative pictures of the matched species, not figures from the paper.

Verbatim
e0“but improved iron humate efficiency”
t0“strategy i plants”
e1“Iron humates exert a long-term effect on the iron fertilization of Strategy I plants in hydroponics (soybean) or soil experiment under controlled conditions as well as in field experiments (tangerines)”
e2“The iron chelate shuttle effect was low”
Claim · model-written summary
HBED/Fe3+ showed slight synergy with iron humates.
- Taxon
- soybean
Glycine maxe1 - Treatment
- iron humates and HBED/Fe3+e0
- Outcome
- slight synergye0
Not reportedDirection
Organisms pictured · Representative pictures of the matched species, not figures from the paper.

Verbatim
e0“a slight synergy between iron humates and HBED/Fe3+ was observed”
t0“strategy i plants”
e1“Iron humates exert a long-term effect on the iron fertilization of Strategy I plants in hydroponics (soybean) or soil experiment under controlled conditions as well as in field experiments (tangerines)”
Claim · model-written summary
Nanofertilizers contributed to iron nutrition.
- Taxon
- soybean
Glycine maxe1 - Treatment
- nanofertilizerse2
- Outcome
- iron nutritione0
Not reportedComparatorDirection
Organisms pictured · Representative pictures of the matched species, not figures from the paper.

Verbatim
e0“Their contribution to iron nutrition was confirmed”
t0“strategy i plants”
e1“Iron humates exert a long-term effect on the iron fertilization of Strategy I plants in hydroponics (soybean) or soil experiment under controlled conditions as well as in field experiments (tangerines)”
e2“the nanofertilizers did not enhance the iron humate efficiency”
Claim · model-written summary
Nanofertilizers were observed in soybean pods.
- Taxon
- soybean
Glycine maxe0 - Outcome
- presence in soybean podse0
Organisms pictured · Representative pictures of the matched species, not figures from the paper.

Verbatim
e0“their presence in soybean pods was observed”
Claim · model-written summary
Nanofertilizers did not enhance iron humate efficiency.
- Taxon
- soybean
Glycine maxe1 - Treatment
- nanofertilizerse0
- Outcome
- iron humate efficiencye0
- Direction
- did not enhancee0
Not reportedComparator
Organisms pictured · Representative pictures of the matched species, not figures from the paper.

Verbatim
e0“the nanofertilizers did not enhance the iron humate efficiency”
t0“strategy i plants”
e1“Iron humates exert a long-term effect on the iron fertilization of Strategy I plants in hydroponics (soybean) or soil experiment under controlled conditions as well as in field experiments (tangerines)”
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